Recovery of hydrocarbons from natural gas



April 18, 1950 RECOVERY OF HYDROCARBONS FROM NATURAL GAS Filed April 18, 1946 2 Sheets-Sheet 1 INVENTOR. J. w. LATCHUM, JR.

BYMMFM ATTORNEYS April 1950 J. w. LATCHUM, JR 2,504,429

RECOVERY OF HYDROCARBONS FROM NATURAL GAS J.W. LATCHUM, JR.

Y ALMI ATTORNEYS Patented Apr. 18, 1950 UNITED STAT-E S" ran T oF -Fi RECOVERYv OE HYDEOGARBONS'zFROMJZi NATURAL GAS .1"

JohnW.-"Latch1im,J1-., Bartlesville, Okla as signor to Phillips Petroleum-*Co'mpanma cor poraticn of :Delaware This invention relates -tolrecoveryof hydro-' carbons from gases. It is particularly adapted-to the recovery of propane and heavier constituents of natural gas by absorption in absorber oil' at" relatively high pressures;followed by'rem'oval of the abscrbedconstitu'ents from the rich oil?" The invention r in certain specific" aspects 1-compriSes-'-* improvements in the desorption steps"whereby important savings-in equipmentand utilitycosts' are realized.

The recovery' 'of natural gasoline from-natural gas by'absorption iniheavyoil is an a1most"uni-' versally' used method in the petroleumindustry: By natural gasoline is meant'not only the normally liquid c'omponents of natural gas, bu'talso the materials known as iliquefi'ed petroleum gases, i. e., propane'and the butanesp: The raw natural gas is passed in contact'witl'ranabsorptionoil e'un-f der conditions'such thatthe absorbin'giiquid takes r up all'the liquid gasoline-fractions, 'essentia'llyeall the" butanes, most of I the propane;iandfismallen amounts of ethane and 'methanewhich areun ri avoidably dissolved: The *undissolved gasis rich?- in methane, and is known ass-residue g'assr This first step of the process is followed'rby a' series'of 1 flashing, stripping, and distillation steps,"the pur pose of which is to cliscardthe'dissolved' methane and ethane, and to recover from the-:rich .oil-the:" propane and" heavier hydrocarbons: The com pleteness of the propane andbutane recovery de:-' pends on economic factorsaffecting agiven-planar. andmay be'varie'd over wide ranges as desiredr Similar procedures may be applied "to -crackedgases, which contain olefins and hydrogensin 'ad dition to the paraffins which 'constitute natural' gas. If the-crackedgas comprises large amounts of normally liquid hydrocarbons,'naph'thenes andr aromatics are also often present;-

The present invention is applicableto'processes'z' of the general nature just described? 'It is espe= 4 cially, though i not exclusivelygadaptedx to the re covery of volatile- -naturalrgasoline; comprising large proportions of the liquefied:petroleum gasesfi from so-called dry.- gases from -high-pressurer "rreservoirs Suchgases, in comparisonwithwet gases,- containrelatively small amounts v of .-pentanes and heavier, but are. richerin'propaneandabutane. Ihe gas is available --at highpressu-res, and the initial absorption is .advantageouslw, effected at a pressure. of, say llcflopoundsperso square inch,-with resultingextractionof highpera centages of methane, ethane, propane,v andlbue tane. Mostof the subsequent stepsior recovery .7 of absorbedhydrocarbons are'conductedat pro- 1 gressively decreasingpressures; but certain stages 2 l require re-compression of vaporsl.tohigh ..pres-wsures.

An important object of this invention, is to re-wv ducethe power requirements for such recom--:--=

-pressions;

Another object is to'effec't the desired-recovery?- of liquefied. hydrocarbons with I less. equipments." thanhas heretofore been'necessary.

A further object is to increase.greatlytheiper-i centage of vapors condensedinthe makeitank of a natural gasoline plant.

Yet another object is to reducelth' volume-;of-.;. stripping still vapors. to be; handled/land; ide phlegmated. I;

A further object is to improve' theeffiiency'of.v a plant for absorbing hydrocarbons from-gases.

Other objectsand advantages of the invention willbe apparent, to one skilled in the "art, from the accompanying disclosure and discussion. v.

The accompanying drawingsoshow somewhat-. diagrammatically one arrangement of apparatus elements and now of materials therethrough... adapted for the practice of my invention. Figo ures 1A and. 1B when joined together present .a single flow sheet of the process. It willb'e app'reciated that various auxiliary items of Japparatus,-.- such as valves and control instruments,--arenot shown in the drawing for the sake of simplicity,'1 as the necessary additional equipmentlmaylbel readily supplied by one skilledin the'art.

In the following description of the drawings, specific operating" data at the various pointsf'are given for one example. It will be understoodlthati the process conditions may be varied over a considerable range as desired I The natural gas from which the heavier .components are to be recovered is introduced .via line lilinto absorber 52, which is operated-at 9,13 pounds persquare inch absolute and F. Into the top'of absorber I2 is introducedlean absorption oil from lean oil surge'tank' l4 Lvia line'llE; pump 58, line 2fl,'line 22 pump 24, 'Iine.26, coolirig I coil 28 and line as; Residue gas, rich in methane, is removed from the" top of abscSrberJI-Zthroughjj: line 32; while .the rich oil is recovered from-the. bottom through line scans passedvintoja first flash tank 35. The pressure is reduced-inlthis tank to 463 pounds per square inch. absdluteandQI the temperature is held at about 100 F. Residue gasis removed through line 38,2and the flashed .o'il is passed via line A8 into. a second flashtankAZQI Tank s2 is operated at a lowered ,pressure whichf o in thelexample being described is 238Ipounds,jand. Y". the" temperature is 100 The'rich oil'whi'ch'has thus been twice flashed passes via line 44 through heat exchanger 46 where it is heated by exchange with lean oil in line 48, and thence through line 50 into the primary vent tank 52. Vapors from the second flash tank 42 are passed through lines 54 and 56 into the reabsorber 58. These vapors are joined by the high stage accumulator vapors and primary vent tank vapors flowing from line 60. Lean oil is passed into the top of reabsorber 58 via line 62, cooling coil 64 and line 66. Residue gas is removed from reabsorber 58 through line 68, while enriched oil is removed from the bottom through line and enters line 44 for admixture with the flashed rich oil from the second flash tank 42. The combined rich oil streams then flow to the primary vent tank 52 as described above. Reabsorber 58 is operated at 100 F. and 233 pounds pressure.

Sufficient heat is imparted in heat exchanger 46 to the flashed rich oil flowing through lines 44 and 50 to bring its temperature to 160 F. The pressure is also reduced so that the pressure in the primary vent tank 52 is 163 pounds. Vapors are withdrawn from this tank by line I2 and passed through a conventional scrubber I4 which serves to remove small amounts of oil. The vapors are then passed through compressor 16, lines I8, and cooling coil 80 into line 60 for passage to the reabsorber in company with the highstage accumulator vapors from line I18. Hot liquid from primary vent tank 52 passes via line 82 into a secondary vent tank 84, being additionallyheated in heat exchanger 86 which is interposed in line 82. Through the other side of heat exchanger 86 flows hot lean oil which has been removed from the bottom of the still 88 through line 80. The secondary vent tank 84 is operated at 270 F. and '75 pounds per square inch absolute pressure. Vapors are withdrawn therefrom via line 92 while the hot partially denuded oil is withdrawn via line 94.

The oil in line 94, which still contains dissolved therein a small amount of methane and ethane, as Well as large amounts of propane, butanes, pentanes, and hexanes and heavier, is passed through the exchanger 96 and preheater 98 before entering the still 88. This still is operated at 58 pounds pressure and 350 F. bottom temperature to drive off the gasoline and lighter vapors, which are removed overhead through line I00. The resulting lean oil is removed from the bottom of still 88 through line 90, and passed as described above through heat exchangers 86 and 46 into the lean oil surge tank l4 for reuse in the absorbers I2 and 58. Into the bottom of still 88 is introduced steam from line I82 to aid in stripping the gasoline hydrocarbons from the absorptio oil.

Up to this point in the process the flow and operating conditions are fairly conventional for a natural gasoline absorption plant. However, in the conventional plant vapors withdrawn from the secondary vent tank 84 through line 92 are passed into admixture with the still vapors in line I00, as by means of a conduit I04 which is indicated in the drawing by a dashed line. This is done because the secondary vent tank vapors are hot, should have about the same condensation characteristics as the still overhead, and usually comprise only a small stream. In the practice of my invention, however, line I04 is not used, and instead the secondary vent tank vapors are passed via line I06 through cooling coil I08, scrubber IIO, line H2 and compressor II4 into line II6 which leads ultimately to the high stage accumulator II8. While line H6 is shown joining with other lines before going through condenser I66 and reaching high stage accumulator II8, the vapors from compressor II4 may be passed directly to condensation and to the high stage accumulator without admixture with other materials if desired, though this is usually much less advantageous as will appear below. The suction pressure for compressor I I4 is 73 pounds in the specific example being described, while the outlet pressure is 243 pounds. By passing the vapors from the secondary vent tank to separate compression and condensation, and bypassing the make tank I48, condensation in tank I48 is greatly enhanced, and total compressor horsepower required to take all the gasolinecontaining streams to the high stage accumulator is reduced. The high methane content of the secondary vent tank vapors in this plant is such that addition of these vapors to the still overhead vapors, as by line I64, would substantially reduce the dew point of the latter.

In my invention, the still overhead vapors in line I00, instead of being joined by a secondary vent tank vapor stream from line 92, are passed alone through heat exchanger 86 and line I20 into dephlegmator I 22, wherein water and absorption oil are condensed. The bulk of the absorption oil is returned to still 88 from dephlegmator I 22 by means of pump I24 and line I26. Part of the water in dephlegmator I22 is removed from the bottom by means of pump I28 and passed through lines I30 and cooling coil I32 into the top of dephlegmator I22 as re flux. The excess water, which represents most of the steam introduced into the bottom of still 88, is passed through line I34 and cooler I36 into oil skimmer I38 and thence through line I40 to any desired use or disposal. Skimmer I38 serves to remove small amounts of heavy absorber oil from the water; the oil is removed through line I39. The dephle'gmated still vapors pass through line I42 to condensing and cooling coil I44 where they are partially condensed, and the resulting mixture of liquid and vapor is passed via line I46 into make tank I48. Small amounts of water are removed from tank I48 through line I 50. Make tank I48 is operated at 53 pounds and F. The liquid is pumped therefrom through line I52 by means of pump I 54 which operates at a discharge pressure of 243 pounds. The vapors from make tank I48, which represent only the lighter ends of the still overhead vapors and are free from the still lighter vapors from the secondary vent tank which would be present in conventional operation, are withdrawn through line I 56 and scrubber I58 into compressor I 60 which increases the pressure from 53 pounds to 243 pounds. These compressed make tank vapors, as well as the liquid being pumped from the make tank, are combined in line I62 for passage to the high stage accumulator II8. This is accomplished by admixture with the compressed secondary vent vapors in line H6 and passage of the entire high pressure mixture through line I64, partial condenser I66, and line I68 into high stage accumulator H8. The compressed make tank vapors from compressor I60 and/or the make tank liquid discharged from pump I54 could be passed to high stage accumulator II8 separately as desired. However, the combination of these streams with the compressed secondary vent tank vapors from line II6 as shown in the drawing, prior to passage mt h wondezuer :lfl, its "much :more efficient sanflisiolhemzererrefi.

s tase accumulator Yell-. 8 is maintained at i238 mounds fiend 90 Vapor-s are withdrawn .thereirom-mrd epassed -hy line .110 "andlineslfio :and '55 to iheireabsorber s58 forrecoveny of sthe more valuable components. Accumulator 448 :is provided avithza mater :drain -I1-l. fIhe raw :gasoline in the high :stagge .raccumulator H18, which soontains zsnia'll amounts of :undesired methane and ethane dissolved therein, withdrawn via line m and passed by means -o'f gpump H4, which discharges zthrongh line JIJJG, -into .-.'irac.tironator 151,8. :Eractionator 4418, which is operated at 250 pounds, .provided with 68. conventional i-"reboiler til Qlreated by :steam ifrom eline 1 82, -'and irom which hondensate is Withdrawn itrom line 484. Jtlapors withdrawn .Jfrom ith'e :top of siractionator 1118 through dine 486 sane passed through condenser rH88 sin'to rrefiux accumulator :L'Sll. eRei'lux is returned ito :the ifractlonator by means of -;line 132 and gpump 1 94, while the light {gases oomprising the Sfractionator :overhead are passed through rline 4 98 to admixture with the "other plant reesidue pas. IIIhe raw natural :gasoline of the plant is withdrawn as bottoms product of firactionator 418 through line l-98 =to cooler 26!], and is ithence zpassed via line 202 to storage or fllrt'her Ztractionation as desired.

order ito further exemplify the invention the liollowing specific data *are provided, which show clearly the differences :and advantages of the naractice -m sthis linvention as icompared with the eon entional practice.

.h planta -constructed and ropemted as described above is "to a atotal sol 25231100 zmots per day of .mw mletggas :ofrthe following composition Component 'Mdl*per-*cent vriitrog en T5121 Methane 72:40 '1 Ethane -"6." 1 Propane lsdbutane Normal butane 'Pentanes Hexanes plus 0539 This is typical of dry gases normally produced from relatively high pressure :gas reservoirs.

The vapor from the secondary vent tank consists of 12,643 mols per day, and has this 'composition:

Component: M01 per cent Methane 12.00 Etimne 1%;65 FPmpane 36;60 itsobutane 8. 1 2 Normal butane s 1735 "Pentanes B507 Hexanes 1plus 1.71

@verhead rl lydrocarbon vapors from the still amount to 12,;432 mols :per day of the tel-lowing composition:

Component: Molper cent Methane 1.37 Ethane "6. 28 Propane i 25. -ilisobu'tane 1 0.150 Normal butane 28560 Pentanes 16.00 Hexanes 11.15

If the plant were operated in accordance with previous standard procedures as outlined above, that is, if the secondary vent tank vapors were joined with 1the :still overhead -mirrors QJBiGr ito :dephlegmation and then "partially icohdensed, the :make tank liquidi'product zwcu'ld resonances mols per day, and would have the ifollowing composition Com onent: Morper'cnt Methane F12 Ethane -1;3a Propane 1 1335 *Is'obutane "K85 Normal butane 26130 Pentanes "126100 lFIexan'es 27111) The recompressor vapors from the make tank in :such la case would aconsist of 21,739 mols :per day .of the following composition:

Component: ll'ildl percent 'Metha'ne "7774 "Ethane 142120 Propane '341W1 Isobutane 935*! Normal butane 22170 Pentanes 8.13 "Hexanes 32 2 In contrast, by operating in accordance with my invention, .the secondary vent tank vapors and the s'till overhead vapors are not admixed but are treatedsepar-ate'ly. The :former, which are normally available sat a pressure of 40 1.0 pounds, are directed to .recompressor H4 for compression and subsequent partial condensation in the high-stageproduct accumulator II L8. Llihe still vapors are alone dephlegmat'ed "and partially The make tank 'uncondensed vapor stream of 6 406 mols "per :day, which :is :passed to the recompressor i 60, has "this composi-tion:

Component: Mo] per cent Methane c iiii "2:62 Ethane i 1 1j1'5 Propane "38.50 Isobutane he- 11:50 Normal butane 26:20 ,Pentanes "7.63 JHexanes 2140 Examination of the foregoing data reveals several very marked and advantageous results of the invention, among the most important of which may be mentioned:

1. By the practice of this invention itis'h'ece'ssary to dephlegmate only 12,432 mols per day, whereas in standard practice 257,075 molsp'er day would have to be handled. 'This difference makes possible a great reduction in the size of the dephl'eema'tor and in the number of condensers or cooling coils.

2. Approximately .5'01per cent of the vapors are condensed in the make tank in my "process, Whereas only 3,336 mo'l's out of a total of 25,075 mols would be condensed in the standard practice. This point is important because in building gasoline plants it is not economically possible to justify the installation of standby recompressors.

As it is impossible for any mechanical equipment to operate one hundred per cent of the time, this recompressor must be down for repairs and as the plant becomes older may fail completely and be down for two or three days before replacement. When this condition arises the make tank vapors are vented to air or into the fuel system and the gasoline production from the plant is limited to the make tank liquid product, which in the present process is nearly twice as great as in the case of standard design.

3. In conventional practice it is necessary to handle 21,739 mols per day through the recompressor with a suction pressure of 15 to 25 pounds per square inch and a discharge pressure of 225 to 250 p. s. i. In the process disclosed herein, however, only 6,406 mols is so handled; this is 15,333 mols per day less than that handled under standard design. Partly offsetting this, however, it is necessary in my process to compress separately in unit 114 an additional 12,643 mols per day of vapors which have never entered the make tank. It is to be noted that this latter volume of vapors is available to 40 to 80 p. s. i. rather than at 15 to 25 p. s. i. as would be the case if the vapors were all being taken from the make tank. Accordingly, in my process a total of only 19,049 mols per day, part of which is available at a higher pressure, must be compressed as compared with 21,739 mols, all available at one low pressure, in standard design. This effects a net saving of about 158 brake horsepower in recompressor installation in favor of my process as shown in the following tabulation:

While certain specific methods of operating have been disclosed herein, it will be appreciated that various modifications can be made without departing from the scope of the invention. To supplement the desired vaporization at any point in the system an added stripping agent; such as steam or low molecular weight gases, may be used. The liberation of dissolved vapors and gases is referred to in the specification and accompanying claims as. vaporization of such components r ebullition of the liquid absorbent in which they are dissolved, and this action may be effected by raising temperature, lowering pres.- sure, use of stripping agents, or any combination thereof.

1 claim:

1. A process for treating natural gas to recover natural gasoline therefrom which comprises passing the gas under pressure countercurrent to a lean absorption oil to dissolve therein gasoline and part of the lighter components including some methane, rejecting undissolved gas, flashing light gases from the resulting rich oil in a first stage by pressure reduction, subjecting the resulting oil without heating to a second pressure reduction to flash additional light gases therefrom, withdrawing said additional light gases and subjecting same to reabsorption bycountercurrent contact with a lean absorption oil, rejecting undissolved gas from said reabsorption step, admixing rich absorption oil from said reabsorption step with the absorption oil from said second pres sure reduction, heating the admixture to a tem perature higher than employed in said first and second pressure reductions and then subjecting the heated oil to a third pressure reduction to vent additional light gases therefrom, passing said additional light gases to contact with absorp tion oil in the aforesaid'reabsorption step, heating flashed rich oil from said third pressurereduction to a still higher temperature; subjecting thus-heated oil to a fourth pressure reductionand separating therefrom a methane-containing gas which if mixed with the still vapors hereinafter described would reduce the percentage of condensate formed when said'vapors aresubjected to partial condensation, subjecting par tially denuded rich oil resulting from said said fourth pressure reduction and whichcont'ains a major proportion of said-gasoline to distillation and dephlegmation to produce as bottom product a lean oil and as overhead product still vapors comprising gasoline hydrocarbons, partially condensing the dephlegmated still vapors to produce a vapor fraction and a liquid fraction, pumping said liquid fraction into' a high-pressure accumulator, compressing and at le'ast partially condensing said vapor fractionand passing same into said high-pressure accumulator; separately cooling and compressing and then partiaIl-y.condensing' the aforesaid methane-containing gas and passing same into said high-pressure accumulator, withdrawing vapors from said highpressure accumulator, and withdrawin liquid from said high-pressure accumulator and fractionating same to recover natural gasoline therefrom as a product of the process.

2. A process according to claim 1 in which said vapor fraction and said methane-containing gas are first separately compressed, and are then admixed and partially condensed.

JOHN W. LATCHUM, JR.

REFERENCES CITED The following references are of record in the file of this patent:

UNITED STATES PATENTS Number Name Date;

1,507,634 Thompson Sept. 9, .1924 1,813,024 Clarke et al July 7, 1931 2,327,896 Houghland Aug. 24, 1943 2,328,829 Maschuitz et a1 Sept. 7, 1943 2,337,254 Legatski et al. Dec. 21, 1943 OTHER REFERENCES Wilson, Refiner and Natural Gasoline Manufacturer, vol. 21, No. 6, pages 70-75, June, 1942.

"Flow Diagram of Lone Star Gasoline Companys Grapeland Recycling Plant, page 126 of The Petroleum Engineer, Nov. 1940.

Braun, Refiner and Natural Gasoline Manufacturer, vol. 11, No. 2, pages 192-495, Feb. 1932.

Oberfell et al., Natural Gasoline," first edition, 1924, pages 241-244.

Certificate of Correction Patent No. 2,504,429 April 18, 1950 JOHN W. LATCHUM, JR.

It is hereby certified that error appears in the printed specification of the above numbered patent requiring correction as follows:

Column 7, line 24, for to, first occurrence, read at; column 8, line 70, list of references cited, for 241-244 read 241244, 260-261 and that the said Letters Patent should be read with this correction therein that the same may conform to the record of the case 1n the Patent Oflice.

Signed and sealed this 5th day of September, A. D. 1950.

[smn] THOMAS F. MURPHY,

Assistant Gammzssz'oner of Patents. 

1. A PROCESS FOR TREATING NATURAL GAS TO RECOVER NATURAL GASOLINE THEREFROM WHICH COMPRISES PASSING THE GAS UNDER PRESSURE COUNTERCURENT TO A LEAN ABSORPTION OIL TO DISSOLVE THEREIN GASOLINE AND PART OF THE LIGHTER COMPONENTS INCLUDING SOME METHANE, REJECTING UNDISSOLVED GAS, FLASHING LIGHT GASES FROM THE RESULTING RICH OIL IN A FIRST STAGE BY PRESSURE REDUCTION, SUBJECTING THE RESULTING OIL WITHOUT HEATING TO A SECOND PRESSURE REDUCTION TO FLASH ADDITIONAL LIGHT GASES THEREFROM, WITHDRAWING SAID ADDITIONAL LIGHT GASES AND SUBJECTING SAME TO REABSORPTION BY COUNTERCURRENT CONTACT WITH A LEAN ABSORPTION OIL, REJECTING UNDISSOLVED GAS FROM SAID REABSORPTION STEP, ADMIXING RICH ABSORPTION OIL FROM SAID REABSORPTION STEP WITH THE ABSORPTION OIL FROM SAID SECOND PRESSURE REDUCTION, HEATING THE ADMIXTURE TO A TEMPERATURE HIGHER THAN EMPLOYED IN SAID FIRST AND SECOND PRESSURE REDUCTIONS AND THEN SUBJECTING THE HEATED OIL TO A THIRD PRESSURE REDUCTION TO VENT ADDITIONAL LIGHT GASES THEREFROM, PASSING SAID ADDITIONAL LIGHT GASES TO CONTACT WITH ABSORPTION OIL IN THE AFORESAID REABSORPTION STEP, HEATING FLASHED RICH OIL FROM SAID THIRD PRESSURE REDUCTION TO A STILL HIGHER TEMPERATURE, SUBJECTING THUS-HEATED OIL TO A FOURTH PRESSURDE REDUCTION AND SEPARATING THEREFROM A METHANE-CONTAINING GAS WHICH IF MIXED WITH THE STILL VAPORS HEREINAFTER DESCRIBED WOULD REDUCE THE PERCENTAGE OF CONDENSATE FORMED WHEN SAID VAPORS ARE SUBJECTED TO PARTIAL CONDENSATION, SUBJECTING PARTIALLY DENUDED RICH OIL RESULTING FROM SAID SAID FOURTH PRESSURE REDUCTION AND WHICH CONTAINS A MAJOR PROPORTION OF SAID GASOLINE TO DISTILLATION AND DEPHLEGMATION TO PRODUCE AS BOTTOM PRODUCT A LEAN OIL AND AS OVERHEAD PRODUCT STILL VAPORS COMPRISING GASOLINE HYDROCARBONS, PARTIALLY CONDENSING THE DEPHLEGMATED STILL VAPORS TO PRODUCE A VAPOR FRACTION AND A LIQUID FRACTION, PUMPING SAID LIQUID FRACTION INTO A HIGH-PRESSURE ACCUMULATOR, COMPRESSING AND AT LEAST PARTIALLY CONDENSING SAID VAPOR FRACTION AND PASSING SAME INTO SAID HIGH-PRESSURE ACCUMULATOR, SEPARATELY COOLING AND COMPRESSING AND THEN PARTIALLY CONDENSING THE AFORESAID METHANE-CONTAINING GAS AND PASSING SAME INTO SAID HIGH-PRESSURE ACCUMULATOR, WITHDRAWING VAPORS FROM SAID HIGHPRESSURE ACCUMULATOR, AND WITHDRAWING LIQUID FROM SAID HIGH-PRESSURE ACCUMULATOR AND FRACTIONATING SAME TO RECOVER NATURAL GASOLINE THEREFROM AS A PRODUCT OF THE PROCESS. 